Overlayer-support interactions associated with the formation of a chemically modified interface: the nickel ferrocyanide derivatized nickel electrode

Abstract

The anodization derivatization of nickel ferrocyanide on a nickel electrode is shown to be sensitive (with respect to surface coverage) to the electrode potential and the electrode crystal face. The epitaxial alignment of the Ni(100) face and the nickel ferrocyanide lattice promotes surface derivatization, while the mismatch of the surface layer and the Ni(lll) face inhibits formation of a surface overlayer. Electrode potential is found to play a dual role. First, the Ni2+ concentration in the interfacial region depends on this parameter; thus both reaction rate and electrode coverage are affected. Second, at higher electrode potentials (>1.0 V vs. SCE), reconstruction of the nickel surface to a surface which promotes epitaxial growth is observed.In the area of electrochemistry, crystal face effects typically are small compared to other phenomena associated with the electrode-electrolyte interface. A major exception to this statement involves submonolayer processes associated with electrodeposition and specific ion adsorption.1 We report here a strong macroscopic crystal face effect associated with the multiple-layer chemical derivatization of the nickel electrode.Recently we reported that polycrystalline nickel electrodes could be chemically derivatized with a nickel ferrocyanide matrix by anodizing the nickel electrode in the presence of aqueous ferricyanide.2 34Electrochemical3-5 and spectroscopic6 investigations of these systems suggested that the surface material consisted of a cubic lattice containing cyanides which bridged iron and nickel centers to generate octahedral sites for both metals in analogy to Prussian Blue. Data available indicated the surface to be

Mechanism for Interplay between Electron and Ionic Fluxes in KhFek[Fe(CN)6]l·mH2O Compounds

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Electroanalytical Detection of Glucose Using a Cyanometalate-Modified Electrode: Requirements for the Oxidation of Buried Redox Sites in Glucose Oxidase

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Comparing electrochemical analysis and particle induced X-ray emission measurements of Prussian Blue Analogue deposits

“…Most literature on the fabrication and study of these materials is based on nanoparticle techniques [21][22][23][24][25][26][27][28][29][30]. In contrast, with an electrochemical method described by Bocarsly and coworkers, the material can be produced directly on an electrode instead of requiring an additional step to bind the material to the electrode [31][32][33][34][35][36][37][38][39].…”